JPS5857436A - Manufacture of water-soluble nitrogen-containing condensate and use for paper manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION In the manufacture of paper and paperboard, polyethyleneimine is used as an auxiliary agent for promoting dewatering and for immobilizing pigments, fine fibers and other anionically reactive additives in the paper. Its use as an agent is already known. However, polyethyleneimine cannot be used as an auxiliary agent in the paper industry unless it is in the neutral and slightly acidic pH range.

Therefore, products have been developed which can be used as dehydration and retention aids even in the acidic l)H range.

Products of this type are produced, for example, by reaction of polyamines with epichlorohydrin (German Patent Application No.
570296).

Furthermore, it is known that retention agents and dehydration aids can be produced by crosslinking polyamidoamines with epichlorohydrin. Crosslinked polyamines are most effective in a neutral pH range, while crosslinked polyamidoamines are most effective in an acidic pH range.

According to German Patent Application No. 1795392, Part 1, there is a process for producing water-soluble crosslinked polyamideamines in which polyamideamines are reacted with trifunctional PL crosslinks produced by reaction of bis-tertiary amines or secondary amines with epichlorohydrin. Known. The water-soluble crosslinked polyamide amine thus obtained can be used as a flocculant, flotation agent and retention agent in the paper industry, and as an aid in the purification of wastewater containing suspended solids. Due to the ti-T of the nitrogen atoms, the efficacy of the water-soluble crosslinked polyamidoamines thus prepared is still unsatisfactory when used as papermaking aids.

According to DE 243 481' 6, polyamidoamines, optionally grafted with ethyleneimine, are combined with α,β-chlorohydrin ethers of polyalkylene oxides having 8 to 100 alkylene oxide units. It is known to produce nitrogen-containing condensation products in which the reaction is carried out just before the formation of a water-soluble product. When used as papermaking aids, these products perform very well even in the acidic and neutral pH range, but their cationic activity is relatively low.

However, for reasons of environmental conservation, the paper industry
The amount of fresh water required per plant should be reduced as much as possible. It therefore tends to make the water circulation within the paper machine more complete. However, this measure results in a significantly higher accumulation of micron11 substances and a concentration of soluble inhibitory substances in the circulating water of the paper machine. For example, this results in intergnathiasis in dehydration and also in the quality of the paper produced. Even with the papermaking aids which have hitherto been well established in practice, this problem which occurs in the closed water circulation within the papermaking machine cannot be solved.

According to DE 30 03 648 A1, water-soluble nitrogen is produced by reacting polyamines, polyamidoamines or polyetheramines with crosslinking agents in aqueous solution at temperatures up to 200° C. to form water-soluble resins. Methods for producing containing condensation products are known. In this case, a condensation product obtained by a two-step reaction of ditertiary diamine with epichlorohydrin and/or dichlorohydrin is used as a crosslinking agent.This condensation product is used as a dehydration aid and retention agent in papermaking. Although they are less susceptible to inhibitors than other dehydration aids, their efficacy needs to be improved.

The object of the present invention is to provide a process for the preparation of water-soluble nitrogen-containing condensation products, which gives a product which exhibits optimum effectiveness in the acidic pH range for use as a retention agent and dewatering aid in papermaking. It was to provide.

The present inventors used (a) 1 mol of a dicarboxylic acid having 4 to 10 carbon atoms as a crosslinking agent in a molecule with 6 to 10 carbon atoms.
(b) condensing the polyamide amine with 1 to 2 moles of a polyalkylene polyamine having 1 to 2 moles of basic nitrogen atoms to form a polyamide amine, and (b) combining this polyamide amine with epichlorohydrin and/or dichlorohydrin in an aqueous solution with p + -14,5
8.5 and 100° C., using a water-soluble reaction product prepared by reacting at temperatures below 8.5 and 100° C., with (a
1 to 160 parts of epichlorohydrin and/or dichlorohydrin per 100 parts by weight of polyamide)
When using parts by weight, ammonia, -class amine, 2
It has now been found that the aforementioned problem is solved by a process for the preparation of water-soluble nitrogen-containing condensation products by reacting polyamines, polyetheramines or polyamidoamines containing ~4 nitrogen atoms with a crosslinking agent. The water-soluble resin thus obtained is used as a retention agent, flocculant, or dewatering aid in paper manufacturing.

The crosslinking agent is produced by a two-step reaction. step (in paulownia, 1 mol of dicarboxylic acid containing 4 to 10 carbon atoms is condensed with 1 to 2 mol of polyalkylene polyamine containing 6 to 10 basic nitrogen atoms in 5 molecules.
A polyamidoamine is obtained. Suitable dicarboxylic acids used for the production of polyamidoamines are succinic acid, maleic acid, adipic acid, glutaric acid, corkic acid, cepatic acid or terephthalic acid. For the production of polyamidoamines, it is also possible to use mixtures of dicarboxylic acids, such as mixtures of adipic acid and glutaric acid or of maleic acid and adipic acid. Preferably adipic acid is used.

Dicarboxylic acids include polyalkylene polyamines containing 3 to 10 basic nitrogen atoms in the molecule, such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetraamine, dihexamethylenetriamine or Condensed with bisaminopropylpiperazine or mixtures thereof. The amine can optionally contain up to 10% by weight of diamylenediamine. The condensation of the dicarboxylic acid with the polyalkylene polyamine is preferably carried out in bulk, with the resulting water being distilled out of the system. The condensation can also be carried out in the presence of lactones or lactams of carboxylic acids having 5>12 carbon atoms. These substances are incorporated into polyamidoamines.

In reaction step (b) for producing the crosslinking agent (second reaction step), the polyamide amine according to reaction step (a) is mixed with epichlorohydrin and/or dichlorohydrin in an aqueous solution at pH 4.5 to 8.5 and 100°C. The reaction is carried out at a temperature of up to The polyamide amine obtained by (revised) was dissolved in water, an inorganic or organic acid was added, and the
Make it H value. The concentration of polyamidoamine in water can vary within a wide range, but is preferably between 20 and 60% by weight. Preferably, the inorganic acids used are hydrochloric acid, sulfuric acid and phosphoric acid, and the organic acids used are, for example, oxalic acid, acetic acid, propionic acid and oxalic acid.

The pH value of the polyamide amine aqueous solution is preferably 5 to 7. The reaction temperature in the second reaction stage is 0 to 100°C, preferably 20 to 60°C.

The reaction of the polyamidoamine with epichlorohydrin and/or dichlorohydrin proceeds practically quantitatively and ends when epichlorohydrin or dichlorohydrin can no longer be detected.

Reaction time is 5 minutes to 3 hours.

For every 100 parts by weight of the polyamidoamine according to step (a), 1 to 130 parts by weight, preferably 10 to 100 parts by weight of epichlorohydrin or dichlorohydrin or a mixture of epichlorohydrin and dichlorohydrin are used.

The polymeric crosslinking agent thus produced is soluble in water. 20 weight of this crosslinking agent:. The viscosity of the aqueous solution is approximately 1 to 10
00 mPa5 preferably 10-100 mPa5 (
(measured at 20°C, respectively).

Polymeric crosslinking agents are used in the process of the invention for crosslinking ammonia, -grade amines, polyamines containing 2 to 4 nitrogen atoms, polyetheramines or polyamidoamines. The reaction is carried out in each case with means containing water-soluble resins. The crosslinking of the l=J H group-containing compounds is carried out in.

Suitable primary amines are, for example, methylamine, ethylamine and propylamine. Examples of polyamines containing 2 to 4 nitrogen atoms are diethylenetriamine, ethylenediamine, triethylenetetraamine, dipropylenetriamine, tripropylenetetraamine, aminopropylethylenediamine and diaminopropylethylenediamine.

Polyether amines can also react with the crosslinking agent to form water-soluble resins. Suitable polyether amines include, for example, 2
1 by reaction of an aliphatic polyamine with a polyevihalogenhydrin containing ~30 halogenmethyl groups (see DE 15 70 296 A1). The polyether amine is a polyglycol containing 2 to 100, preferably 8 to 50 ethylene oxide units in the terminal OH group as α,6)-dichlorohydrin ether, which corresponds more to epichlorohydrin; It can also be obtained by subsequently reacting this with polyamines, ammonia or amines. Another method is to react polyglycol ether with acrylonitrile and hydrogenate the resulting reaction product.

Another class of compounds that can react with polymeric crosslinkers are basic polyamidoamines, ie polyamidoamines having free NH and NH2 groups. In this case, the steps for the production of polymeric crosslinkers as above (at K the condensation products described as well as oligoamines or polyamines and
Polyamidoamines obtained by condensation of I-C20-monocarboxylic acids are involved. However, ethylene is also suitable.

According to the method of the invention, preferably ammonia and ethylene, diamines and mixtures of these compounds are subjected to reaction with a polymeric crosslinking agent. It should be noted that the ratio of the polymeric crosslinker to the compound reacting with it can be varied within a wide range, in which case only water-soluble compounds are obtained. ioo per part by weight, polymer crosslinking agent is 98~
2 parts by weight, preferably 5°C to 95 parts by weight. The condensation reaction can be carried out continuously or discontinuously. To produce a water-soluble nitrogen-containing condensation product, for example, the compound to be crosslinked is charged to a reactor and about 1 to 6
0% and heated one reactor mixture to 40-100'C;
Additional polymeric crosslinking agent can be added continuously or in portions as consumed. However, when crosslinking ammonia and low-boiling amines, it is also possible to mix the polymeric crosslinker and the compound to be crosslinked and slowly heat the mixture to the reaction temperature. Alternatively, the reaction can be carried out under increased pressure, for example up to 100 bar, preferably between 2 and 10 bar. In other embodiments, a reaction vessel is first charged with 5-60% of the mixture of the polymer crosslinker and at least one compound to be crosslinked, the mixture is then heated to reaction temperature, and the polymer crosslinker The remainder of the mixture from the compound to be crosslinked with is added as the reaction progresses. The compound to be crosslinked with the polymeric crosslinker (NH group-containing compound) can also be fed separately to the reaction zone. If the viscosity of the reaction mixture in the condensation becomes so high that the reaction components cannot be easily mixed, the reaction mixture can be diluted by addition of a solvent, preferably water.

Depending on the reaction conditions (temperature and concentration of reactants), the condensation reaction is complete after about 60 minutes to 15 hours. The condensation is 100% measured as a 20% aqueous solution at 20°C.
The process is continued to the extent that a water-soluble polymer resin having a viscosity of mPa5 or more -L is obtained. Preferably, a resin is produced whose 20% aqueous solution has a viscosity of 400 to 2500 mPa5 at 20°C. The progress of the crosslinking reaction can be easily followed by taking a sample from the reaction mixture and measuring its viscosity under certain conditions. Preferably, the solution concentration is selected such that a resin solution with a resulting content of 5 to 60% by weight results.

The water-soluble nitrogen-containing condensation products thus produced are used in papermaking as retention agents, flocculants and dewatering aids. The reaction mixture can be used for papermaking directly after production, necessarily after dilution with water. The pH value of the aqueous solution of the reaction mixture is preferably 7. -5 to 10 range. The water-soluble nitrogen-containing condensation product is preferably 0.01 to 0.3% of the dry fiber material in papermaking. compared to the drug. The dehydration-promoting effect was shown by a decrease in clarity in 'SR. 7 Jotsupah/
The freeness according to the Riederer was determined according to the instructions of Merckblatt 107 of the Vereins der Soerstof Hemikerland Papier Hemiker und Ingenür. Unless otherwise specified in the examples below,
The viscosity is described using a Hague rotating disk viscometer.
These are the results measured with a 20% by weight aqueous solution at ℃, and 1
It was adjusted to a shear rate of 4977 seconds for the viscosity range below 000 +nR+s and a shear force of 24.5 parts seconds on J7.

The retention effect of the filler material was determined by the amount of ash in the paper sheets produced in the Ravidköten apparatus according to Melkblatt 108 of Vereins der @ Zershtnov Hemikärland Väperähemiker Land Ingenür. Specific talent. , Preparation of the crosslinking agent: Crosslinking agent ■ In a heatable vessel equipped with a stirrer, a thermometer and a descending condenser, diethylenetriamine yio.

50 parts of water and 161 parts of adipic acid are mixed. As soon as the adipic acid has dissolved, the clear solution is heated to 190° C. for 6 hours under a nitrogen atmosphere. During this time, first the added water and then the water produced in the condensation reaction is distilled off. After a condensation time of 4 hours at 190 DEG C., the melt is cooled to 50 DEG C. under reduced pressure of 10 mbar. When 285.5 parts of water is added to the highly viscous polyamide amine at this temperature, an aqueous resin solution is obtained. The solid matter content of the aqueous solution is 42.9% (measured by rolling 0.5 g of resin at 120'C in a dry box for 2 hours) and the viscosity is 1050 mPa5.
(Measured at 25°C using a Hepler viscometer and ball drop method). The acid value for 100% resin is 3°74 and the basic nitrogen content is 6.2%. The 1% resin solution is 2
'IQ has a relative viscosity of 0°159 at 25°C in saline.

Step of crosslinking agent production (l for bl, 4 for holamidoamine)
2.9 100 parts of an aqueous solution are brought to pH 7.5 at 65° C. with 6.9 parts of 67.2% hydrochloric acid. 65 for this
12 parts of epichlorohydrochloride 9 were added over 5 minutes at 65 °C, and the solution was stirred for 5 minutes at 65 °C.
By adding the seventh part, the pH value of the reaction mixture is brought to 5. Addition of parts iii and a of water gives an aqueous solution of crosslinker I with a concentration of 20% (calculated without chloride). The solid content of the resin solution (measured by drying 0.5 g of the resin solution at 120.degree. C. within 2 hours) is 23.6%. Emission time (Ford cup, 4 mm nozzle) is 12.9 seconds.

Crosslinking Agent■ In a heated 5-filter vessel equipped with a stirrer, thermometer and descending condenser, 200 parts (1 mol) of bisaminopropylpiperazine, 87 parts (0.5 mol) of cepacic acid and 100 parts of water were added. Mix and heat to 190°C for 6 hours. During this time, the water produced by the condensation reaction is distilled off.
7). After a condensation time of 4 hours at 190° C., the melt is cooled to 130° C. under reduced pressure of 10 mbar. Adding 251 parts of water to the melt at this temperature gives a 50% low viscosity resin solution.

In step (b) of cross-linking agent production, 100 parts of a 50% resin solution is adjusted to pH 1 with 195 parts of concentrated hydrochloric acid (57.2%) at 65°C.
Make it 5. Add to this 27.6 liters of epichlorohydrin for 5 minutes.
1.5 min and the reaction mixture was stirred at 65°C for 15 minutes.

188 parts of water are then added, resulting in an aqueous solution of crosslinking agent (1) with a solids content of 20% (calculated without chloride).

Production of water-soluble resin: Example 1 18 parts of ethylenediamine was added to 18 parts of ethylenediamine at 70°C for 1.5 hours.
478.4 parts of an aqueous solution of Crosslinker I are added. The pH value of the reaction mixture is maintained between 9 and 95 by adding 50% aqueous sodium hydroxide solution. The total amount of caustic soda aqueous solution is 65.2
It takes a long time. As the addition of the crosslinking agent proceeds, the reaction mixture gradually becomes viscous. The crosslinking agent is added until the reaction mixture no longer drips from the immersed glass rod but becomes stringy. The viscous solution was then heated for 1 hour at 70
After stirring at °C, cool to room temperature.

The reaction mixture is brought to pH 8 by addition of oxalic acid (>24.6 parts, 98%). The polymer solution is then treated with 2.3 parts of a 5% aqueous solution of sulfur bisulfite and 0.0 parts of a 5% aqueous solution of hydroxylammonium hydrochloride. 46 parts are added.A water-soluble nitrogen-containing resin is obtained in the form of an aqueous solution with a polymer content of 20.6% (chloride-free calculation) and a dry matter content of 295% (measured as above). Its viscosity is 473 +nP
It is a5.

Example 2 177 parts of crosslinking agent I was added to 100 parts of 27% aqueous ammonia.
The mixture is heated to 65° C. for 60 minutes and a further 40.7 parts of an aqueous solution of crosslinker I are added over the course of 1 hour. By adding 50.degree. aqueous caustic soda solution, the 1)) value is brought to 93 during the condensation. After the addition of the crosslinking agent has ended, the reaction mixture is stirred for another 1.5 hours at 65° C. and then brought to pH 8 by addition of 5 parts of 97% oxalic acid.

For stabilization, the reaction mixture is mixed with 0.18 parts of 40% sodium bisulfite solution and 0.06 parts of 50% hydroxylammonium chloride solution. Water-soluble nitrogen-containing resin has a polymer content of 18.6% (calculated without chloride)
has. The outflow time of the Ford cup (4 mm nozzle) is 1 minute 4 seconds. 20% resin aqueous solution is 600 mPa
It has a viscosity of 5 (measured by rotating bowl ≠ viscometer).

Example 6 1590 parts of an aqueous solution of crosslinking agent I are added to a mixture of 296 parts of 1,8-diamino-6,6-thioxaoctane and 48 parts of ethylenediamine at 50° C. over 6 hours. 50
The pH value of the reaction mixture is maintained between 9 and 95 by adding % aqueous sodium hydroxide solution. Therefore, a total of 117 parts of 50% caustic soda aqueous solution is required. As the addition of cross-linking agent progresses,
The mixture will gradually become viscous. After the addition of the crosslinker was complete, the reaction mixture was stirred for another hour at 70°C and then heated to 90°C.
The pH value of the reaction mixture is brought to 8 by addition of 7% oxalic acid. The water-soluble nitrogen-containing resin has a polymerization potency of 21.2'iA -6;- (calculated on a chloride-free basis). The viscosity of a 2016 aqueous solution of this resin is 625 mPa5.

Example 4 In a heatable container equipped with a stirrer and a thermometer, a mixture of 20 parts of ethylene ref.
Mix with 149 parts of an aqueous solution of at 25°C. The reaction mixture is then heated to 65°C for 15 minutes. The pH value is adjusted to 9 by addition of 50% aqueous caustic soda solution (for this purpose 68
). During the course of a further 6 hours, an additional 15.5 parts of crosslinker H dissolved in water were added, the pH value being brought to 9 by addition of 42 parts of 50% aqueous caustic soda solution.
~95 1. As the addition of crosslinking agent progresses, the viscosity of the reaction solution increases.

After the addition of the crosslinker has ended, the reaction mixture is stirred for another hour at 65°C and then cooled to 20°C. 21.6
An aqueous solution of nitrogen-containing resin with a polymer content of 2% (calculated without chloride) is obtained. The pH value of the solution is 9.

The viscosity of a 20% aqueous solution (by rotating handle ≠ viscometer) is 70
0 mPa5.

Comparative Example 1 (Example according to German Patent Application No. 2 434 816) 100 parts of a 20% aqueous solution of polyamidoamine from diethylenetriamine and adipic acid modified with ethyleneimine were heated to 60° C. and 2.05 mol of epichlorohydrin was added. Crosslinking is effected by adding 40.5 parts of a 20% aqueous solution of a crosslinking agent from a polyglycol ether of molecular weight 1500 reacted with a polyglycol ether until a polymeric product is formed. The crosslinking reaction lasts 650 minutes. After this time,
A 20% aqueous solution gives a condensation product with a viscosity of 830 mPa5 at 25'C.

Comparative Example 2 (according to Example 6 of German Patent Application No. 3003648) The polyamidoamine resin modified with ethyleneimine according to Comparative Example 1 was condensed with a crosslinking agent obtained by a two-step reaction of piperazine with epichlorohydrin,
In that case, the molar ratio of piperazine to epichlorohydrin is 1:0.75 in the first reaction step and the pH value is 10-10.
．． 5 and in the second reaction step, at pH 7, epichlorohydrin is added at a molar ratio of piperazine to epichlorohydrin of 1:1.25. 20° of polyamidoamine reacted with this crosslinker and modified by ethyleneimine. The viscosity of the aqueous solution was approximately 800 mPa5.

Testing of the application properties of the resins produced according to the Examples and Comparative Examples: The materials obtained according to the Examples and Comparative Examples were tested with regard to their effectiveness as dehydration aids and retention agents 1'). In order to characterize the dehydration-promoting properties of the material, the reduction in the freeness, indicated by 'SR, in the slurrying of the fibrous material obtained by disintegrating newsprint in an Ultra-Toorax device is useful. Table 1 shows a summary of the measured values. Each numerical value listed in the table is an average value from eight measurements. Measurements were carried out at pH 7.6 in the absence of alum and at pH 4.8 in the presence of 1.5% alum. The zero value is the control value obtained without adding resin to the fibrous material.

Table 1 Dehydration test 1 test pH value 76 4.8
Zero value 72.5°SR69°SR Example 1 (0sR) 56 5o
58 54 Example 2 ('S■() 5
4 50.5 59, 56 Example 3 (
0sR) 54 49 58.
5 55.5 Example 4 ('5R)-555059,5
5 Comparative Example 1 (0SE() 56 51
61.5 58 Comparative Example 2 (0SR)
55 50 60.5 57.5 In Examples 1 to 4 and Comparative Example 1, in order to test the resin retention effect by +S2,
A fibrous material slurry consisting of 80% 5R) and 20% filler (China clay) was used. The filler retention effect is due to the resin content of 0.015%, 0.06% and 0.045=δ in the paper stock.
. was added and measured. Retention values were determined at pH 6 (0.5% alum addition to the fiber material) and at pH 4.5 (1.5% alum addition). Zero values were determined without the addition of dehydration aids and retention agents. The values obtained for charge retention are shown in Table 2.

Table 2 pH 6 of fiber suspension Amount used (%) 0.015 0.05 Retention property measured by ash content in paper (%) Zero value (%) 4.1 Addition of resin according to the following example (%) Examples -18,79,8 Example 2 8.3 9 Example 3 8.6
9.7 Implementation Example 4
8.5 9.1 Comparative Example 1 7.5 8
．． 6 Comparison Example 2 7.8
8.24.8 0.045 0.015 0. G3 0.
0454.5 11J 8.5 9.5 11
．． 510.8 8.3 9.0
10.811.1 8.0 9.1
10.311.0 8.1 9.1
10.510.3 7.0
8.4 10.010.5 7.3
8.8 10.1 Applicant Basf Akchengesellschaft Agent Patent Attorney Masao Kobayashi Continued from page 1 ■ Applicant Basf Akchengesellschaft Federal Republic of Germany 6700 Ludwigshalfen Karl-Botschustler Se38

Claims (1)

[Claims] 1. As a crosslinking agent, (a) 1 mol of a dicarboxylic acid having 4 to 10 carbon atoms is added to a polyalkylene polyamine having 6 to 10 basic nitrogen atoms in ~2
mol to form a polyamide amine, and (l
]) This polyamide amine is treated with epichlorohydrin and/or
or using a water-soluble reaction product prepared by reacting dichlorohydrin in an aqueous solution with pH 4,5 to 85 and 100' at temperatures of: 100 parts by weight of the polyamide amine according to (a); Ammonia, -class amine,
Process for producing a water-soluble nitrogen-containing condensation product by reacting a polyamine, polyetheramine or polyamidoamine containing 2 to 4 nitrogen atoms with a crosslinking agent. 2. Claim 1. A method of using the water-soluble nitrogen-containing condensation product produced by the method described in 1. as a retention agent, flocculant, or dewatering aid in paper manufacturing.